EP0068807B1 - Bains acides pour dépôt électrolytique de cuivre comportant des agents de brillantage et de nivellement - Google Patents

Bains acides pour dépôt électrolytique de cuivre comportant des agents de brillantage et de nivellement Download PDF

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Publication number
EP0068807B1
EP0068807B1 EP82303273A EP82303273A EP0068807B1 EP 0068807 B1 EP0068807 B1 EP 0068807B1 EP 82303273 A EP82303273 A EP 82303273A EP 82303273 A EP82303273 A EP 82303273A EP 0068807 B1 EP0068807 B1 EP 0068807B1
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acid copper
copper electroplating
electroplating bath
carbon atoms
formula
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German (de)
English (en)
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EP0068807A3 (en
EP0068807A2 (fr
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Angus Alexander Watson
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M&T Chemicals Inc
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M&T Chemicals Inc
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

  • This invention is concerned with the electrodeposition of copper from aqueous acidic baths. More particularly this invention is concerned with an aqueous acidic bath for the electrodeposition of copper containing additives which provide bright and leveled copper electrodeposits and to a process for electrodepositing copper employing said bath.
  • the present invention has as its object the formation of bright and leveled copper electrodeposits from an aqueous acidic bath, particularly an aqueous acidic sulfate bath by adding to such bath certain additives.
  • leveled denotes a copper deposit whose surface is smoother than its substrate.
  • opaque indicates that the formed electrodeposit is characterized by having a uniform highly reflective surface gloss over most of its surface.
  • leveling and brightness vary with the current density at the cathode, all other factors such as copper salt concentration, pH, type of acid, temperature etc. being equal. As the current density decreases brightness of the electrodeposit tends to decrease often diminishing to a haze which may be unacceptable for many commercial applications.
  • the strength of leveling also varies with current density.
  • the present invention provides bright copper electrodeposits over a wide current density range including low current densities on the order of 0.4 amp. sq. dm. or less with strong leveling properties throughout.
  • the high degree and rate of leveling achieved according to the present invention translates to economy in the finishing costs of the electrodeposited substrate and in the materials necessary therefor.
  • the improved low current density brightness, that is the widening of the bright current density range, according to the invention allows strongly profiled objects to be electroplated with substantially uniform brightness.
  • the additives also prevent roughness formation at high current densities and increase hardness of the electrodeposit.
  • the additive of DE-B-1,151,159 is obtained by condensing a polyfunctional amine with epichlorohydrin to give a derivative with reactive amino group(s), which are then reacted with carbon disulfide in the presence of alkali hydroxide, and the dithiocarbamic acid derivatives thus obtained are esterified.
  • FR-A-1,481,435 the use is proposed of 2-imidazolidinethione and water-soluble derivatives of 2-imidazolidinethione and 2-thiazolidinethione, together with other organic brightening agents, such as the N,N-dimethyl-dithiocarbamate derivative of n-propyl-3-sulfonate.
  • the additive of US-A-3,328,273 is a polyether together with a sulfide compound containing a terminal sulfonic acid group.
  • the additives of this invention comprise:
  • the alkylated polyalkyleneimine additive of this invention is obtained by first reacting a polyalkyleneimine with an epihalohydrin, preferably epichlorohydrin, in about equal molar ratios.
  • the maximum molecular weight of the polyalkyleneimine is about 215.
  • Typical polyalkyleneimines include ethylene diamine propylene diamine, diethylene triamine, dipropylene triamine and the like.
  • the reaction product of the polyalkyleneimine and epihalohydrin is then neutralized with a base such as NaOH.
  • a base such as NaOH.
  • an alkylating agent such as an alkyl halide having from 1 to 3 carbon atoms, an alkylene halide having from 3 to 6 carbon atoms, an alkynyl halide having from 3 to 6 carbon atoms, or an aralkyl halide such as benzyl chloride.
  • An organic sulfonate such as propane sultone or a halopropyl sulfonate may also be used as the alkylating agent.
  • Benzyl chloride is particularly preferred as the alkylating agent. There is no evidence of the formation of quaternary nitrogens by the alkylating agent.
  • the organic sulfo sulfonate additive of this invention contains the structural moieties wherein R' is a divalent hydrocarbon, M is an alkali metal or ammonium cation and n" is a number greater than 1.
  • organic sulfonates can be represented by the formula: wherein M is an alkali metal or ammonium ion; n" is from 1 to 6; R' is an alkylene group of from 1 to 8 carbon atoms, a divalent aromatic hydrocarbon or an aliphatic aromatic hydrocarbon of 6 to 12 carbon atoms; R 1 is a group represented by the formula M0 3 SR', wherein M & R' are as described above, wherein R 2 & R 3 are each hydrogen or an alkyl group having from 1 to 4 carbon atoms, wherein r is from 2 to 6;
  • Typical organic sulfo sulfonates include compounds of the following classes:
  • Typical polyethers are listed in Table 1 below:
  • the thioorganic additives of this invention are those containing the structural formula: or its tautomeric form:
  • These tautomeric groups may be a part of a non-cyclic molecule such as an open chain thiourea in which they become a part of the wider groups or they may be a part of a heterocyclic ring structure further containing carbon atoms or carbon atoms and one or more 0, N or S atoms in which case they become part of the wider groups.
  • (H) is a heterocyclic ring as described above.
  • the thioorganic compounds may also be contained in heterocyclic rings in non-tautomeric forms such as wherein (H) is as described above and (A) is an aromatic nucleus.
  • the thioorganic compounds of this invention can be represented by the formula: wherein the bond between C and S and N and C is a single or a double bond, R1 or R 2 ' may be hydrogen or R 1 ' taken together with R 2 ' forms a heterocyclic ring structure of 5 to 6 members or a benzo-substituted heterocyclic ring structure of 5 to 6 members wherein said ring members are comprised totally of carbon atoms or carbon atoms and at least one S, N or N-substituted atom, R3 is hydrogen alkyl, aralkyl, and R4 is wherein R 5 and R 6 are each hydrogen, alkyl or aralkyl groups.
  • thiourea and N-alkyl and aryl-substituted thioureas such as dimethyl, diethyl and benzyl substituted thioureas, 2-thiaz b lidinethione 2-imidazolinethione, and benzothiazolethione
  • Particularly preferred is an equimolar mixture of 2-thiazolidinethione and 1-(2-hydroxyethyl)-2-imidazolidine thione.
  • the alkylated polyalkyleneimines in combination with the organic sulfo sulfonates, and polyethers in an acid copper electroplating bath give bright copper deposits over a wide current density range with strong leveling properties.
  • the amount of alkylated polyalkyleneimine added to the acid copper plating bath should vary from .0001 to 0.1 g/I of bath and preferably from 0.001 to 0.05 g/I.
  • the amount of organo sulfo sulfonate compound should be between 0.001 to 0.1 g/I and preferably from .010 to .050 g/I.
  • the amount of polyether additive should be between 0.005 g/I and 10.0 g/I and preferably from 0.010 to 1.0 g/I.
  • the amount of thioorganic compound should be between 0.0001 and 0.100 g/I and preferably from 0.001 to 0.050 g/I.
  • Typical aqueous acidic copper plating baths in which the additives of this invention may be contained include the following: The additives of this invention may also be employed in acid copper fluoroborate baths.
  • a standard 267 ml Hull Cell was employed in each Example using as the cathode a brass panel given a standard scratch with 0/4 emery paper and preplated with a copper strike and a copper anode.
  • the current employed was 2 amperes for 10 minutes which gave a range of current densities of from about 0.1 amps./ sq.dm. to 15.0 amps./sq.dm. across the cathode. All experiments were run at room temperature using air agitation.
  • the alkylated polyalkyleneimine was prepared by combining 20.6 g of diethylene triamine (0.2 mole), with 91 ml water in a 250 ml round bottomed flask. To this combination was slowly added 18.5 g (0.2 mole) of epichlorohydrin at a rate sufficient to maintain the exothermic reaction temperature below about 130°F. After all the epichlorohydrin was added, the reaction mixture was refluxed 2 hrs. The reaction mixture was then cooled and 20 ml of 10N NaOH (0.2 mole) was added to neutralize the solution. To this neutralized solution was added 25.5 g (0.2 mole) of benzyl chloride and refluxed for 4 hours. A straw-colored gum precipitated. After decanting off the aqueous layer the alkylated polyalkyleneimine residue was separated. There was no evidence of quaternary nitrogen formation. z
  • the panels, after electrodeposition, were found to be fully bright and well leveled above 0.6 amp. sq. dm.
  • the panel exhibited a bright, well leveled copper deposit over most of the Hull Cell current density range.
  • a bright copper deposit in the high current density range (greater than 4 amp. sq. dm. was obtained).
  • a bright and well-leveled copper deposit was obtained above about 0.4 amp. sq. dm.
  • polyether and alkylated polyalkylene imine was added 0.001 g/I of a thioorganic compound, N-ethyl thiourea.
  • the resulting deposit was bright, ductile and had good leveling above about 0.8 amp. sq. dm.
  • an alkylated polyalkyleneimine was prepared by reacting a polyethyleneimine having a molecular weight greater than about 215 with epichlorohydrin and benzylchloride.
  • an alkylated polyalkyleneimine prepared by reacting a polyethyleneimine having a molecular weight no greater than about 215 with epichlorohydrin and benzyl chloride When tested for leveling properties in an acid copper bath it was less satisfactory than an alkylated polyalkyleneimine prepared by reacting a polyethyleneimine having a molecular weight no greater than about 215 with epichlorohydrin and benzyl chloride.
  • a quaternary polyalkyleneimine was prepared by reacting a polyalkyleneimine having a molecular weight of about 600 with propylene oxide to form a propoxylated intermediate and then quaternerizing the intermediate with benzyl chloride using a 5 fold molar excess of benzyl chloride.
  • This product when tested as a leveler in an acid copper bath exhibited good leveling properties but no as good as the leveling properties of Additive 1.
  • Example 1 non-quaternerized polyalkyleneimine.
  • the quaternerized polyalkyleneimine also gave a cloudy area on the plate at low current densities.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Chemically Coating (AREA)
  • Paints Or Removers (AREA)
  • Electrolytic Production Of Metals (AREA)

Claims (15)

1. Bain acide pour dépôt électrolytique de cuivre contenant une polyalcoylèneimine alcoylée obtenue en alcoylant encore le produit réactionnel d'une polyalcoylèneimine représentée par la formule:
Figure imgb0072
où R est H ou (CH2)n―NH2 et n et n' son indépendamment égaux à 1 à 6, avec une épihalohydrine.
. 2. Bain acide de cuivre de la revendication 1 où ladite polyalcoylèneimine set choisie parmi l'éthylène diamine, la propylène diamine, la diéthylène triamine et la dipropylène triamine.
3. Bain acide de cuivre de la revendication 1 ou la revendication 2 où ledit agent alcoylant est choisi parmi un halogénure d'alcoyle ayant de 1 à 3 atomes de carbone, un halogénure d'alcoylène ayant de 3 à 6 atomes de carbone, un halogénure d'alkynyle ayant de 3 à 6 atomes de carbone et un halogénure d'aralcoyle.
4. Bain acide pour dépôt électrolytique de cuivre selon l'une quelconque des revendications précédentes qui contient de plus un sulfo sulfonate organique représenté par la formule:
Figure imgb0073
où M est un ion d'un métal alcalin ou d'ammonium; n" est compris entre 1 et 6; R' est choisi parmi un groupe alcoylène ayant 1 à 8 atomes de carbone, un hydrocarbure aromatique divalent et un hydrocarbure aliphatique-aromatique contenant 6 à 12 atomes de carbone; R1 est choisi dans le groupe M03SR' où M et R' sont décrits ci-dessus,
Figure imgb0074
dans laquelle chacun de R2 et R3 est hydrogène ou un groupe alcoyle ayant de 1 à 4 atomes de carbone,
Figure imgb0075
où r est compris entre 2 et 6.
5. Bain acide pour dépôt électrolytique de cuivre selon la revendication 4 où ledit sulfo sulfonate organique est un disulfo sulfonate représenté par la formule:
Figure imgb0076
où a est compris entre 2 et 6.
6. Bain acide pour dépôt électrolytique de cuivre de la revendication 4 où ledit sulfo sulfonate organique est un dialkyl dithiocarbamate sulfoné représenté par la formule:
Figure imgb0077
où chacun de Ra peut être un groupe alcoyle de 1 à 3 atomes de carbone ou un hydrocarbure cycloaliphatique et b est'un nombre compris entre 2 et 6.
7. Bain acide pour dépôt électrolytique de cuivre de la revendication 4 où ledit sulfo sulfonate organique est
Figure imgb0078
8. Bain acide pour dépôt électrolytique de cuivre de la revendication 4 où ledit sulfo sulfonate organique est
Figure imgb0079
9. Bain acide pour dépôt électrolytique de cuivre selon l'une quelconque des revendications précédentes qui contient de plus un polyéther représenté par la formule:
Figure imgb0080
où R" est choisi parmi l'hydrogène, un alcoyle, un alkényle, un alkynyle, un alcoylaryle et arylalcoyle; m est compris entre 5 et 100; et
Figure imgb0081
où u et v = 0 à 4 mais au moins l'un de u et v doit être supérieur à 0, r + s = 6 à 200.000; r = 0 lorsque u = 0; s = 0 lorsque v =0; et T est choisi parmi l'hydrogène, un alcoyle et du benzyle.
10. Bain acide pour électrolytique de cuivre selon l'une quelconque des revendications précédentes qui contient de plus un composé thioorganique représenté par la formule:
Figure imgb0082
où la liaison entre C et S et N et C est une simple ou une double liaison,
Figure imgb0083
 peut êtree hydrogène ou bien
Figure imgb0084
pris avec
Figure imgb0085
forme une structure d'un noyeau hétérocyclique de 5 à 6 membres ou une structure d'un hoyau hétérocyclique benzo-substitué de 5 à 6 membres où lesdits membres du noyau se composent totalement d'atomes de carbone ou d'atomes de carbone et d'au moins un hétéroatome choisi parmi un atome de S, N et N-substitué, R3 est choisi parmi l'hydrogène, un alcoyle et un arlacoyle et
Figure imgb0086
 est
Figure imgb0087
où chacun de Rs et R6 est choisi parmi l'hydrogène, des groupes alcoyle et aralcoyle.
11. Bain acide pour dépôt électrolytique de cuivre selon l'une quelconque des revendications précédentes où ladite épihalohydrine est l'épichlorohydrine.
12. Bain acide pour dépôt électrolytique de cuivre selon l'une quelconque des revendications précédentes où ladite polyalcoylèneimine alcoylée est formée de quantités sensiblement équimolaires d'un agent alcoylant et du produit réactionnel d'une polyalcoylèneimine et d'épichlorohydrine.
13. Bain acide pour dépôt électrolytique de cuivre selon l'une quelconque des revendications précédentes où ledit composé thioorganique est choisi parmi le thiourée, des thiourées N-alkyle et aryle- substituées, la 2-thiazolidinethione, la 1-(2-hydroxyéthyl)-2-imidazolidine thione, le 2-aminothiazole, la 2-imidazoline thion, la 2-mercaptopyridine et la benzothiazolethione.
14. Bain acide pour dépôt électrolytique de cuivre selon l'une quelconque des revendications précédentes où ledit composé thioorganique se compose d'un mélange équimolaire de 2-thiazolidinethione et de 1-(2-hydroxyéthyl)-2-imidazolidine thione.
15. Bain acide pour dépôt électrolytique de cuivre contenant:
(a) Une polyalcoylèneimine alcoylée obtenue en tant que produit réactionnel d'une polyalcoylèneimine représentée par la formuale:
Figure imgb0088
où R est H ou (CH2)n,NH2 et n et n' sont indépendamment égaux à 1 à 6. avec de l'épichlorohydrine et du chlorure de benzyle, les quantités molaires de la polyalcoylèneimine, de l'épichlorohydrine et du chlorure de benzyle étant sensiblement égales.
(b) un sulfo sulfonate organique représenté par la formule:
Figure imgb0089
où a est compris entre 2 et 6;
(c) un polyéther représenté par la formule:
Figure imgb0090
où R est choisi parmi l'hydrogène, un alcoyle, un alkényle, un alkynyle, un alcoylaryle et un arylalcoyle; m est compris entre 5 et 100; et
Figure imgb0091
où u etv = 0 à 4 mais au moins l'un de u et v doit être supérieur à 0, r + s = 6 à 200.000; r = 0 lorsque u = 0; s = 0 lorsque v = 0; et T est choisi parmi l'hydrogène, un alcoyle et le benzyle;
(d) une combinaison équimolaire de 2-thiazolidine-thione et de 1-(2-hydroxyéthyl)-2-imidazolidinethione.
EP82303273A 1981-06-24 1982-06-23 Bains acides pour dépôt électrolytique de cuivre comportant des agents de brillantage et de nivellement Expired EP0068807B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82303273T ATE26312T1 (de) 1981-06-24 1982-06-23 Saure glanzmittel und einebnungsmittel enthaltende baeder zum elektrolytischen aufbringen von kupfer.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/277,057 US4376685A (en) 1981-06-24 1981-06-24 Acid copper electroplating baths containing brightening and leveling additives
US277057 1981-06-24

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EP0068807A2 EP0068807A2 (fr) 1983-01-05
EP0068807A3 EP0068807A3 (en) 1984-07-25
EP0068807B1 true EP0068807B1 (fr) 1987-04-01

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US (1) US4376685A (fr)
EP (1) EP0068807B1 (fr)
JP (1) JPS583991A (fr)
AT (1) ATE26312T1 (fr)
AU (1) AU548506B2 (fr)
CA (1) CA1194832A (fr)
DE (1) DE3275936D1 (fr)

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EP0068807A3 (en) 1984-07-25
DE3275936D1 (en) 1987-05-07
EP0068807A2 (fr) 1983-01-05
US4376685A (en) 1983-03-15
AU8389482A (en) 1983-01-06
CA1194832A (fr) 1985-10-08
JPS583991A (ja) 1983-01-10
ATE26312T1 (de) 1987-04-15
JPH0340113B2 (fr) 1991-06-17
AU548506B2 (en) 1985-12-12

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